Correlations between shadow glass transition, enthalpy recovery and medium range order in a Pd40Ni40P20 bulk metallic glass

Two distinct enthalpic states were induced in a Pd40Ni40P20 bulk metallic glass through cyclic annealing at 473 K (0.81Tg) and 558 K (0.96Tg), targeting individual β or α relaxation modes, here referred to as the so-called shadow glass transition (SGT) and enthalpy recovery, respectively. Fluctuation electron microscopy (FEM) was employed to systematically investigate the medium-range order (MRO) within the amorphous structure in the post-annealed state and subsequent quenching after the SGT. Comparing the results with literature data from the same glass quenched from SCL samples, a significant increase in MRO was observed after annealing at 0.81Tg. Conversely, samples quenched directly after the SGT exhibit a reduced MRO, similar to those quenched from the supercooled liquid (SCL). These findings suggest a correlation between the SGT and a decrease in MRO within the glass, a phenomenon discussed in the context of underlying structural rearrangements associated with β relaxation, encompassing the SGT Yang et al. (2020). Additionally, prolonged annealing at 0.96Tg led to glass separation in the material, with remixing observed as an endothermic transformation in the SCL. The origin of this transformation is discussed as either a potential liquid-liquid or glass-liquid transition and their connection to modifications in medium-range order.